Connect public, paid and private patent data with Google Patents Public Datasets

Naphthenic acid corrosion inhibitors

Download PDF

Info

Publication number
US5182013A
US5182013A US07631422 US63142290A US5182013A US 5182013 A US5182013 A US 5182013A US 07631422 US07631422 US 07631422 US 63142290 A US63142290 A US 63142290A US 5182013 A US5182013 A US 5182013A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
corrosion
naphthenic
acid
polysulfide
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07631422
Inventor
Philip R. Petersen
Frederick P. Robbins, III
William G. Winston
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab Inc
Original Assignee
ExxonMobil Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00Distillation of hydrocarbon oils
    • C10G7/10Inhibiting corrosion during distillation

Abstract

Naphthenic acid corrosion in refinery distillation units is inhibited by introducing into the units effective amounts of a polysulfide corrosion inhibitor.

Description

FIELD OF THE INVENTION

This invention relates generally to a process for inhibiting naphthenic acid corrosion in refining operations. In one aspect, the invention relates to the use of a polysulfide corrosion inhibitor for inhibiting naphthenic acid corrosion in crude distillation units and furnaces.

BACKGROUND OF THE INVENTION

Corrosion problems in petroleum refining operations associated with naphthenic acid constituents in crude oils have been recognized for many years. Such corrosion is particularly severe in atmospheric and vacuum distillation units at temperatures between 400 degrees F. and 790 degrees F. Other factors that contribute to the corrosivity of crudes containing naphthenic acids include the amount of naphthenic acid present, the presence of sulfides, the velocity and turbulence of the flow stream in the units, and the location in the unit (e.g., liquid vapor interface).

Efforts to minimize or prevent the naphthenic corrosion have included the following approaches:

(a) blending of higher naphthenic acid content oil with oil low in naphthenic acids;

(b) neutralization and removal of naphthenic acids from the oil; and

(c) use of corrosion inhibitors.

The problems caused by naphthenic acid corrosion in refineries and the prior art solutions to that problem have been described at length in the literature, the following of which are representative:

1) "Naphthenic Acid Corrosion in Crude Distillation Units," by R. L. Piehl, published in Materials Performance, January, 1988;

2) "Naphthenic Acid Corrosion, An Update of Control Methods," by Scattergood et al, Paper No. 197, presented in Corrosion/87, San Francisco, Mar. 9-13, 1987; and

3) "Studies Shed Light on Naphthenic Acid Corrosion," by J. Gutzeit, published in the Oil and Gas Journal, Apr. 5, 1976.

Because these approaches have not been entirely satisfactory, the accepted approach in the industry is to construct the distillation unit, or the portions exposed to naphthenic acid corrosion, with resistant metals such as high quality stainless steel or alloys containing higher amounts of chromium and molybdenum. However, in units not so constructed there is a need to provide corrosion inhibition treatment against naphthenic acid. The prior art corrosion inhibitors for naphthenic acid environments include amine and amide based corrosion inhibitors. As stated in the NACE publication (Paper No. 197) identified above, these corrosion inhibitors are relatively ineffective in the high temperature environment of naphthenic acid oils.

SUMMARY OF THE INVENTION

It has surprisingly been discovered that organic polysufides are effective naphthenic acid corrosion inhibitors for refinery distillation units. The corrosion inhibitor may be introduced into the oil upstream of the furnaces to provide protection for the furnace tubes as well as the distillation units. Also, the inhibitor may be added to a reflux recycle stream that is returned to the atmospheric or vacuum distillation tower above the area that is experiencing naphthenic acid corrosion. This treated liquid will then descend in the tower, protecting all metal surfaces it comes into contact with.

The amount of the corrosion inhibitor in the oil should be sufficient to provide as much protection as possible against corrosive effects of the acids in the oil. The economics, however, dictate that the percent protection with reasonable levels of treatment is greater than about 40% and preferably from 50 to 80%. (Percent protection is defined below).

The concentration of the corrosion inhibitor will generally range from 10 to 5000 ppm, preferably between to 25 to 2000 ppm and most preferably between 100 and 1500 ppm, based on the weight of the feed stream. The organic polysufides are particularly effective in the treatment of crude oil containing corrosive amounts of naphthenic acids and hydrogen sulfide.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Many crude oils contain corrosive amounts of naphthenic acid. The concentration of naphthenic acid in crude oil is expressed as an acid neutralization number or acid number which is the number of milligrams of KOH required to neutralize the acidity on one gram of oil. Crude oils with acid numbers of about 1.0 and below are considered low to moderately corrosive. Crudes with acid numbers greater than 1.5 are considered corrosive and require treatment or the use of corrosion resistant alloys.

In the distillation refining of crude oils, the crude oil is passed successively through a furnace, and one or more fractionators such as an atmospheric tower and a vacuum tower. In most operations, naphthenic acid corrosion is not a problem at temperatures below about 400 degrees F. As mentioned previously, the amine and amide corrosion inhibitors are not effective at these high temperatures and the other approaches for preventing naphthenic acid corrosion such as neutralizing present operational problems.

It should be observed that the term "naphthenic acid" includes mono and di basic carboxylic acids and generally constitutes about 50 percent by weight of the total acidic components in crude oil. Naphthenic acids may be represented by the following formula: ##STR1## Where: R is an alkyl or cycloalkyl and n ranges generally from 2 to 10.

Many variations of this structure and molecular weight are possible.

Naphthenic acids are corrosive between the range of about 210 degrees C. (400 degrees F.) to 420 degrees C. (790 degrees F.). At the higher temperatures the naphthenic acids are in the vapor phase and at the lower temperatures the corrosion rate is not serious. The corrosivity of naphthenic acids appears to be exceptionally serious in the presence of sulfides, such as hydrogen sulfide.

It has been discovered that by incorporating an effective amount of organic polysulfide, the corrosivity of naphthenic acids at the elevated temperatures is substantially reduced, even in the presence of hydrogen sulfide.

The polysulfides usable in the present invention have the following formula:

R--Sx--R'

Where: R and R' are each an alkyl group containing from 6 to 30 carbon atoms, or cycloalkyl group containing from 6 to 30 carbon atoms and 1 to 4 rings or an aromatic group; and x ranges from 2 to 6.

The preferred polysulfides are those in which the R and R' groups are the alkyl and cycloalkyl groups. The most preferred polysulfides are those wherein both R and R' groups are the same (e.g., alkyl groups or cycloalkyl groups).

The sulfur content of the polysulfide ranges from 10 to 60%, preferably 25 to 50%, by weight. The preferred polysulfides include the following: olefin polysulfides and terpene polysulfides or mixtures thereof.

The molecular weight of the polysulfides useable in the method of the present invention may range from 200 to 800, preferably 300 to 600.

The organic polysulfides can be prepared by processes well known in the art. See for example U.S. Pat. Nos. 2,708,199 and 3,022,351 and 3,038,013, the disclosures of which are incorporated herein by reference. Also, see Chapter 22 entitled "Inorganic and Organic Polysulfides" of Sulfur in Organic and Inorganic Chemicals, by Alexander Senning, published by Marcell Dekker (1972).

The polysulfides are soluble in a variety of oils and therefore may be introduced as an oil soluble package. Preferred carriers are aromatic solvents such as xylenes and heavy aromatic naphtha. Other additives such as surfactants or other types of corrosion inhibitor may be included in the package. Generally, the polysulfide will constitute from 20 to 70 weight % of the package.

LABORATORY EXPERIMENTS

A series of laboratory experiments were conducted to demonstrate the effectiveness of the organic polysulfides as naphthenic acid corrosion inhibitors.

Test Equipment:

1. temperature controlled autoclave

2. cylindrical coupons (mild steel)

3. means to rotate the coupon to provide a peripheral velocity in excess of 10 FPS

Materials:

1. lubricating oil with naphthenic acid added to provide a neutralization no. of 11.

2. nitrogen in the vapor space.

The following samples were prepared and tested:

______________________________________                   ConcentrationSample   Corrosion Inhibitor                   (PPM)______________________________________A-1      Organic polysulfide'                   1000A-2      Organic polysulfide.sup.'                   500A-3      Organic polysulfide'                   250B-1      Organic polysulfide"                   1000B-2      Organic polysulfide"                   500B-3      Organic polysulfide"                   250X        Prior Art Corrosion                   1000    Inhibitor'"______________________________________ 'Aliphatic Polysulfide "Alicyclic Polysulfide "'Imidazoline

Table I presents the results of the corrosion coupon tests. The vapor space contained only nitrogen. The results are based on the average of two coupons exposed for a period of 18 hours at a temperature of 400 degrees F. The percentage protection is based on the following calculation: ##EQU1## Wo=weight loss of untreated blank coupon Wi=weight loss of inhibited coupon

              TABLE I______________________________________Corrosion InhibitorSample     Concentration (PPM)                     Protection______________________________________A-2         500           31B-1        1000           67B-2         500           31X          1000           15______________________________________

A comparison of the organic polysulfide performance with the commercial amine corrosion inhibitor reveals that the polysulfides more than doubled the percent protection at half the concentration. At comparable concentrations the organic polysulfide increased percent protection by more than 400% (Sample B-1 versus Sample X tests).

Table II presents the results of corrosion coupon tests carried out for 18 hours at 400 degrees F. where the vapor phase contained nitrogen with 4 percent hydrogen sulfide.

              TABLE II______________________________________Corrosion InhibitorSample     Concentration (PPM)                     % Protection______________________________________Blank       0             0A-1        1000           58A-2        500            63A-3        250            0B-1        1000           80B-2        500            0B-3        250            0X          1000           0______________________________________

In the severe corrosive environment of naphthenic acid and hydrogen sulfide, the commercial amine corrosion inhibitor gave no protection. The organic polysulfides above 250 ppm, however, gave surprisingly good protection (58-80%). It should be noted that the scattering of data are common in corrosion tests. It should be observed that laboratory coupon tests are generally carried out at higher concentrations than those used in practice. Although test with Samples A-3 and B-3 (250 ppm) did not demonstrate protection in the laboratory, concentrations at this range and even smaller would be expected to provide protection because of the continuous chemical injection with time can build up a protective film on the metal.

Table III presents the results of corrosion coupon tests for 18 hours at a temperature of 500 degrees F. wherein the vapor phase contained nitrogen with 4 percent hydrogen sulfide.

              TABLE III______________________________________Corrosion InhibitorSample     Concentration (PPM)                     % Protection______________________________________Blank      --              0A-1        1000           27A-2        500            46B-1        1000           37B-2        500            70______________________________________

The organic polysulfides provided reasonable protection under the most severe test conditions (500 degrees F. in the presence of hydrogen sulfide.)

The following conclusions can be drawn from the test results presented in Tables I-III:

1. The commercial amine corrosion inhibitor (Sample X gave practically no protection against naphthenic acid corrosion in the presence or absence of hydrogen sulfide.)

2. The organic polysulfide corrosion inhibitors were far more effective inhibitors than the commercial inhibitor and exhibited activity up to temperatures of 500 degrees F.

Although the reasons for the improved results are not fully understood, it is believed that the high sulfur content of the organic polysulfides contributes to inhibition properties by forming a more protective iron sulfide/polysulfide film on the metal surface.

Claims (7)

What is claimed is:
1. A method of inhibiting naphthenic acid corrosion of crude oil in a crude oil distillation unit carried out at a temperature above 400 degrees F., said method comprising introducing into the oil an effective amount of an organic polysulfide to inhibit naphthenic acid corrosion, said polysulfide having the following formula:
R--(S)x--R'
where: R and R' are each alkyl groups having from 6 to 30 carbon atoms, or a cycloalkyl group having from 6 to 30 carbon atoms, or an aromatic group, and may be the same or different; and x ranges from 2 to 6.
2. The method of claim 1 wherein the concentration of the organic polysulfide in the oil stream is between 25 to 2000 ppm.
3. The method of claim 2 wherein the R and R' are each alkyl or cycloalkyl groups.
4. The method of claim 1 wherein the percent sulfur in the polysulfide comprises from 10 to 60 wt % of the polysulfide.
5. A method of inhibiting naphthenic acid corrosion in a vacuum distillation unit which comprises continuously introducing into the vacuum distillation unit an effective amount of an organic polysulfide within the concentration range of 10 ppm to 5000 ppm based on the feed stream into the unit to substantially reduce the naphthenic acid corrosion in the unit.
6. A method of treating a refinery distillation tower for processing oil containing corrosive amounts of naphthenic acid and hydrogen sulfide carried out at temperatures within the range of 400 to 790 degrees F., said method comprising the step of introducing into the oil processed through the tower inhibiting amounts of an organic polysulfide having the following formula:
R--(S)x--R'
where: R is and R' are each al alkyl or cycloalkyl group containing from 6 to 30 carbon atoms; and x ranges from 2 to 6.
7. The method of claim 6 wherein the concentration of organic polysulfides in the oil is between 100 to 1500 ppm based on the weight of the oil.
US07631422 1990-12-21 1990-12-21 Naphthenic acid corrosion inhibitors Expired - Lifetime US5182013A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US07631422 US5182013A (en) 1990-12-21 1990-12-21 Naphthenic acid corrosion inhibitors
EP19930300295 EP0607640B1 (en) 1990-12-21 1993-01-18 Naphtenic acid corrosion inhibitors
JP2474993A JP2971691B2 (en) 1990-12-21 1993-01-20 Inhibitor of naphthenic acid corrosion

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US07631422 US5182013A (en) 1990-12-21 1990-12-21 Naphthenic acid corrosion inhibitors
ES93300295T ES2106959T3 (en) 1990-12-21 1993-01-18 Corrosion inhibitors caused by naphthenic acids.
DE1993612901 DE69312901T2 (en) 1990-12-21 1993-01-18 Naphtensäurekorrosionsschutzmittel
DE1993612901 DE69312901D1 (en) 1990-12-21 1993-01-18 Naphtensäurekorrosionsschutzmittel
EP19930300295 EP0607640B1 (en) 1990-12-21 1993-01-18 Naphtenic acid corrosion inhibitors
JP2474993A JP2971691B2 (en) 1990-12-21 1993-01-20 Inhibitor of naphthenic acid corrosion

Publications (1)

Publication Number Publication Date
US5182013A true US5182013A (en) 1993-01-26

Family

ID=27235365

Family Applications (1)

Application Number Title Priority Date Filing Date
US07631422 Expired - Lifetime US5182013A (en) 1990-12-21 1990-12-21 Naphthenic acid corrosion inhibitors

Country Status (5)

Country Link
US (1) US5182013A (en)
JP (1) JP2971691B2 (en)
DE (2) DE69312901D1 (en)
EP (1) EP0607640B1 (en)
ES (1) ES2106959T3 (en)

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5314643A (en) * 1993-03-29 1994-05-24 Betz Laboratories, Inc. High temperature corrosion inhibitor
EP0607640A1 (en) * 1990-12-21 1994-07-27 Exxon Chemical Patents Inc. Naphtenic acid corrosion inhibitors
US5464525A (en) * 1994-12-13 1995-11-07 Betz Laboratories, Inc. High temperature corrosion inhibitor
EP0742277A2 (en) * 1995-05-10 1996-11-13 Nalco Chemical Company Use of sulfiding agents for enhancing the efficacy of phosphorus in controlling high temperature corrosion attack
GB2304730A (en) * 1995-08-25 1997-03-26 Exxon Research Engineering Co Process for neutralization of petroleum acids using alkali metal trialkylsilanolate
US5683626A (en) * 1995-08-25 1997-11-04 Exxon Research And Engineering Company Process for neutralization of petroleum acids
US5863415A (en) * 1996-05-30 1999-01-26 Baker Hughes Incorporated Control of naphthenic acid corrosion with thiophosporus compounds
US6022494A (en) * 1995-08-25 2000-02-08 Exxon Research And Engineering Co. Process for decreasing the acid content and corrosivity of crudes
US6030523A (en) * 1997-05-30 2000-02-29 Exxon Research And Engineering Co. Process for neutralization of petroleum acids (LAW810)
US6054042A (en) * 1995-08-25 2000-04-25 Exxon Research And Engineering Co. Process for neutralization of petroleum acids using overbased detergents
US6063347A (en) * 1998-07-09 2000-05-16 Betzdearborn Inc. Inhibition of pyrophoric iron sulfide activity
US6121411A (en) * 1997-12-17 2000-09-19 Exxon Research And Engineering Company Process for decreased the acidity of crudes using crosslinked polymeric amines (LAW871)
US6228239B1 (en) 1999-02-26 2001-05-08 Exxon Research And Engineering Company Crude oil desalting method
US6258258B1 (en) 1998-10-06 2001-07-10 Exxon Research And Engineering Company Process for treatment of petroleum acids with ammonia
US6281328B1 (en) 1999-08-06 2001-08-28 Exxonmobil Research And Engineering Company Process for extraction of naphthenic acids from crudes
US6328943B1 (en) * 1998-07-09 2001-12-11 Betzdearborn Inc. Inhibition of pyrophoric iron sulfide activity
US6673238B2 (en) * 2001-11-08 2004-01-06 Conocophillips Company Acidic petroleum oil treatment
US20040026299A1 (en) * 2002-07-05 2004-02-12 Chamberlain Pravia Oscar Rene Process for reducing the naphthenic acidity of petroleum oils
WO2005040313A1 (en) * 2003-10-17 2005-05-06 Fluor Technologies Corporation Compositions, configurations, and methods of reducing naphthenic acid corrosivity
FR2868787A1 (en) * 2004-04-13 2005-10-14 Arkema Sa Use of organic polysulphides against corrosion by crude acids
US20060043003A1 (en) * 2004-08-26 2006-03-02 Petroleo Brasileiro S.A. - Petrobras Process for reducing the acidity of hydrocarbon mixtures
US20060157387A1 (en) * 2003-07-07 2006-07-20 Francis Humblot Method for prevention of corrosion by naphthenic acids in refineries
US20060201855A1 (en) * 2005-03-10 2006-09-14 Petroleo Brasileiro S.A.-Petrobras Process for reducing the naphthenic acidity of petroleum oils or their fractions
US20070056880A1 (en) * 2005-09-15 2007-03-15 Petroleo Brasileiro S.A. - Petrobras Process for reducing the acidity of hydrocarbon mixtures
US20070108099A1 (en) * 2004-02-06 2007-05-17 Francis Humblot Method for corrosion control of refining units by acidic crudes
WO2008122989A2 (en) 2007-04-04 2008-10-16 Dorf Ketal Chemicals (I) Private Limited Naphthenic acid corrosion inhibition using new synergetic combination of phosphorus compounds
US20080257782A1 (en) * 2007-04-18 2008-10-23 General Electric Company Corrosion assessment method and system
WO2009063496A2 (en) 2007-09-14 2009-05-22 Dorf Ketal Chemicals (I) Private Limited A novel additive for naphthenic acid corrosion inhibition and method of using the same
WO2010023628A1 (en) 2008-08-26 2010-03-04 Dorf Ketal Chemicals (I) Pvt. Ltd. An effective novel polymeric additive for inhibiting napthenic acid corrosion and method of using the same
US20100051510A1 (en) * 2008-08-27 2010-03-04 Seoul National University Industry Foundation Magnetic nanoparticle complex
US20100126842A1 (en) * 2007-03-30 2010-05-27 Dorf Ketal Chemicals (I) Private Limited High temperature naphthenic acid corrosion inhibition using organophosphorous sulphur compounds and combinations thereof
US20110155558A1 (en) * 2009-12-30 2011-06-30 Petroleo Brasileiro S.A.-Petrobras Process for reducing naphthenic acidity & simultaneous increase of api gravity of heavy oils
US20110214980A1 (en) * 2008-08-26 2011-09-08 Mahesh Subramaniyam New additive for inhibiting acid corrosion and method of using the new additive
EP2628780A1 (en) 2012-02-17 2013-08-21 Reliance Industries Limited A solvent extraction process for removal of naphthenic acids and calcium from low asphaltic crude oil
US20150210928A1 (en) * 2011-10-18 2015-07-30 Baker Hughes Incorporated Method for reducing hydrogen sulfide evolution from asphalt and heavy fuel oils
CN105220158A (en) * 2014-06-19 2016-01-06 中石化洛阳工程有限公司 Non-phosphor high-temperature inhibitor and preparation method thereof
US9637689B2 (en) 2011-07-29 2017-05-02 Saudi Arabian Oil Company Process for reducing the total acid number in refinery feedstocks
US9777230B2 (en) 2009-04-15 2017-10-03 Dorf Ketal Chemicals (India) Private Limited Effective novel non-polymeric and non-fouling additive for inhibiting high-temperature naphthenic acid corrosion and method of using the same

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060091044A1 (en) 2004-11-02 2006-05-04 General Electric Company High temperature corrosion inhibitor
US7588664B2 (en) * 2005-07-27 2009-09-15 Chicago Bridge & Iron Company Oil distillation vacuum column with thickened plate in the vapor horn section
FR2946055B1 (en) 2009-05-29 2012-08-03 Total Raffinage Marketing Method for reduction of naphthenic acidity of petroleum feedstocks and use
JP5421794B2 (en) * 2010-01-12 2014-02-19 日揮株式会社 Crude oil processing system
GB201120391D0 (en) 2011-11-25 2012-01-11 Petroliam Nasional Berhad Petronas Corrosion inhibition
CN102559263B (en) * 2011-12-13 2014-03-12 浙江杭化科技有限公司 High temperature corrosion inhibitor for oil refining device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2973316A (en) * 1957-07-12 1961-02-28 Union Oil Co Process for preventing corrosion in ferrous systems
CA701194A (en) * 1965-01-05 B. Thompson Ralph Process for inhibiting metal corrosion
US3989459A (en) * 1969-09-24 1976-11-02 Nippon Oil Company Ltd. Method of preventing corrosion of steelworks

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2034643A (en) * 1933-06-01 1936-03-17 Texas Co Motor fuel
US2385158A (en) * 1941-09-06 1945-09-18 Standard Oil Dev Co Hydrocarbon fuel blends
GB579369A (en) * 1943-02-09 1946-08-01 Standard Oil Dev Co Improvements in or relating to non-corrosive hydrocarbon fuels and solvents
US2614914A (en) * 1946-06-04 1952-10-21 Standard And Oil Dev Company Diesel fuel containing di-tertiary alkyl sulfides as ignition promoters
GB629543A (en) * 1946-11-25 1949-09-22 Standard Oil Dev Co Improvements in or relating to fuels for gas turbine and jet propulsion engines
US3062612A (en) * 1959-04-25 1962-11-06 Inst Francais Du Petrole Method of protecting metals against electrochemical corrosion of the acidic type
GB1421108A (en) * 1973-09-07 1976-01-14 Exxon Research Engineering Co Sulphurised phenols
DE3437936A1 (en) * 1984-10-17 1986-04-17 Peter Siegfried Process and agent for combating corrosion under reducing conditions
US5182013A (en) * 1990-12-21 1993-01-26 Exxon Chemical Patents Inc. Naphthenic acid corrosion inhibitors

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA701194A (en) * 1965-01-05 B. Thompson Ralph Process for inhibiting metal corrosion
US2973316A (en) * 1957-07-12 1961-02-28 Union Oil Co Process for preventing corrosion in ferrous systems
US3989459A (en) * 1969-09-24 1976-11-02 Nippon Oil Company Ltd. Method of preventing corrosion of steelworks

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CA113(16): 135548g, Mar. 9, 1990. *

Cited By (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0607640A1 (en) * 1990-12-21 1994-07-27 Exxon Chemical Patents Inc. Naphtenic acid corrosion inhibitors
US5314643A (en) * 1993-03-29 1994-05-24 Betz Laboratories, Inc. High temperature corrosion inhibitor
US5464525A (en) * 1994-12-13 1995-11-07 Betz Laboratories, Inc. High temperature corrosion inhibitor
EP0742277A2 (en) * 1995-05-10 1996-11-13 Nalco Chemical Company Use of sulfiding agents for enhancing the efficacy of phosphorus in controlling high temperature corrosion attack
US5630964A (en) * 1995-05-10 1997-05-20 Nalco/Exxon Energy Chemicals, L.P. Use of sulfiding agents for enhancing the efficacy of phosphorus in controlling high temperature corrosion attack
EP0742277A3 (en) * 1995-05-10 1998-02-25 Nalco/Exxon Energy Chemicals L.P. Use of sulfiding agents for enhancing the efficacy of phosphorus in controlling high temperature corrosion attack
US6054042A (en) * 1995-08-25 2000-04-25 Exxon Research And Engineering Co. Process for neutralization of petroleum acids using overbased detergents
GB2304730A (en) * 1995-08-25 1997-03-26 Exxon Research Engineering Co Process for neutralization of petroleum acids using alkali metal trialkylsilanolate
US5643439A (en) * 1995-08-25 1997-07-01 Exxon Research And Engineering Company Process for neutralization of petroleum acids using alkali metal trialkylsilanolates
US6022494A (en) * 1995-08-25 2000-02-08 Exxon Research And Engineering Co. Process for decreasing the acid content and corrosivity of crudes
US5683626A (en) * 1995-08-25 1997-11-04 Exxon Research And Engineering Company Process for neutralization of petroleum acids
US5863415A (en) * 1996-05-30 1999-01-26 Baker Hughes Incorporated Control of naphthenic acid corrosion with thiophosporus compounds
US6030523A (en) * 1997-05-30 2000-02-29 Exxon Research And Engineering Co. Process for neutralization of petroleum acids (LAW810)
US6121411A (en) * 1997-12-17 2000-09-19 Exxon Research And Engineering Company Process for decreased the acidity of crudes using crosslinked polymeric amines (LAW871)
US6063347A (en) * 1998-07-09 2000-05-16 Betzdearborn Inc. Inhibition of pyrophoric iron sulfide activity
US6328943B1 (en) * 1998-07-09 2001-12-11 Betzdearborn Inc. Inhibition of pyrophoric iron sulfide activity
US6258258B1 (en) 1998-10-06 2001-07-10 Exxon Research And Engineering Company Process for treatment of petroleum acids with ammonia
US6228239B1 (en) 1999-02-26 2001-05-08 Exxon Research And Engineering Company Crude oil desalting method
US6281328B1 (en) 1999-08-06 2001-08-28 Exxonmobil Research And Engineering Company Process for extraction of naphthenic acids from crudes
US6673238B2 (en) * 2001-11-08 2004-01-06 Conocophillips Company Acidic petroleum oil treatment
US20040026299A1 (en) * 2002-07-05 2004-02-12 Chamberlain Pravia Oscar Rene Process for reducing the naphthenic acidity of petroleum oils
US20060283781A1 (en) * 2002-07-05 2006-12-21 Petroleo Brasileiro S.A. Process for reducing the naphthenic acidity of petroleum oils
US7504023B2 (en) 2002-07-05 2009-03-17 Petroleo Brasileiro S.A. Process for reducing the naphthenic acidity of petroleum oils
US20060157387A1 (en) * 2003-07-07 2006-07-20 Francis Humblot Method for prevention of corrosion by naphthenic acids in refineries
US7491318B2 (en) 2003-07-07 2009-02-17 Arkema France Method for prevention of corrosion by naphthenic acids in refineries
US20080164137A1 (en) * 2003-10-17 2008-07-10 Fluor Corporation Compositions, Configurations, and Methods of Reducing Naphtenic Acid Corrosivity
CN1894389B (en) 2003-10-17 2011-11-09 弗劳尔科技公司 Compositions, configurations, and methods of reducing naphthenic acid corrosivity
WO2005040313A1 (en) * 2003-10-17 2005-05-06 Fluor Technologies Corporation Compositions, configurations, and methods of reducing naphthenic acid corrosivity
US8118994B2 (en) * 2003-10-17 2012-02-21 Fluor Technologies Corporation Compositions, configurations, and methods of reducing naphtenic acid corrosivity
US20070108099A1 (en) * 2004-02-06 2007-05-17 Francis Humblot Method for corrosion control of refining units by acidic crudes
FR2868787A1 (en) * 2004-04-13 2005-10-14 Arkema Sa Use of organic polysulphides against corrosion by crude acids
WO2005103208A1 (en) * 2004-04-13 2005-11-03 Arkema France Use of organic polysulfides against corrosion by acid crudes
US20070163922A1 (en) * 2004-04-13 2007-07-19 Francis Humblot Use of organic polysulfides against corrosion by acid crudes
US20060043003A1 (en) * 2004-08-26 2006-03-02 Petroleo Brasileiro S.A. - Petrobras Process for reducing the acidity of hydrocarbon mixtures
US7507329B2 (en) 2005-03-10 2009-03-24 Petroleo Brasileiro S.A. - Petrobras Process for reducing the naphthenic acidity of petroleum oils or their fractions
US20060201855A1 (en) * 2005-03-10 2006-09-14 Petroleo Brasileiro S.A.-Petrobras Process for reducing the naphthenic acidity of petroleum oils or their fractions
US20070056880A1 (en) * 2005-09-15 2007-03-15 Petroleo Brasileiro S.A. - Petrobras Process for reducing the acidity of hydrocarbon mixtures
US7514657B2 (en) 2005-09-15 2009-04-07 Petroleo Brasiliero S.A - Petrobras Process for reducing the acidity of hydrocarbon mixtures
US20100126842A1 (en) * 2007-03-30 2010-05-27 Dorf Ketal Chemicals (I) Private Limited High temperature naphthenic acid corrosion inhibition using organophosphorous sulphur compounds and combinations thereof
US9090837B2 (en) 2007-03-30 2015-07-28 Dorf Ketal Chemicals (I) Private Limited High temperature naphthenic acid corrosion inhibition using organophosphorous sulphur compounds and combinations thereof
WO2008122989A2 (en) 2007-04-04 2008-10-16 Dorf Ketal Chemicals (I) Private Limited Naphthenic acid corrosion inhibition using new synergetic combination of phosphorus compounds
US9228142B2 (en) 2007-04-04 2016-01-05 Dorf Ketal Chemicals (I) Private Limited Naphthenic acid corrosion inhibition using new synergetic combination of phosphorus compounds
US20100116718A1 (en) * 2007-04-04 2010-05-13 Dorf Ketal Chemicals (1) Private Limited Naphthenic acid corrosion inhibition using new synergetic combination of phosphorus compounds
US20080257782A1 (en) * 2007-04-18 2008-10-23 General Electric Company Corrosion assessment method and system
WO2008130809A1 (en) * 2007-04-18 2008-10-30 General Electric Company Corrosion assessment method and system
US7818156B2 (en) 2007-04-18 2010-10-19 General Electric Company Corrosion assessment method and system
US20100264064A1 (en) * 2007-09-14 2010-10-21 Dorf Ketal Chemicals (1) Private Limited novel additive for naphthenic acid corrosion inhibition and method of using the same
WO2009063496A2 (en) 2007-09-14 2009-05-22 Dorf Ketal Chemicals (I) Private Limited A novel additive for naphthenic acid corrosion inhibition and method of using the same
US9115319B2 (en) 2007-09-14 2015-08-25 Dorf Ketal Chemicals (I) Private Limited Additive for naphthenic acid corrosion inhibition and method of using the same
US20110160405A1 (en) * 2008-08-26 2011-06-30 Dorf Ketal Chemicals (1) Private Limited Effective novel polymeric additive for inhibiting napthenic acid corrosion and method of using the same
US20110214980A1 (en) * 2008-08-26 2011-09-08 Mahesh Subramaniyam New additive for inhibiting acid corrosion and method of using the new additive
WO2010023628A1 (en) 2008-08-26 2010-03-04 Dorf Ketal Chemicals (I) Pvt. Ltd. An effective novel polymeric additive for inhibiting napthenic acid corrosion and method of using the same
US8157986B2 (en) 2008-08-27 2012-04-17 Seoul National University Research & Development Business Foundation Magnetic nanoparticle complex
US8366916B2 (en) 2008-08-27 2013-02-05 Seoul National University Research & Development Business Foundation (“SNU R&DB Foundation”) Magnetic nanoparticle complex
US20100051510A1 (en) * 2008-08-27 2010-03-04 Seoul National University Industry Foundation Magnetic nanoparticle complex
US9777230B2 (en) 2009-04-15 2017-10-03 Dorf Ketal Chemicals (India) Private Limited Effective novel non-polymeric and non-fouling additive for inhibiting high-temperature naphthenic acid corrosion and method of using the same
US20110155558A1 (en) * 2009-12-30 2011-06-30 Petroleo Brasileiro S.A.-Petrobras Process for reducing naphthenic acidity & simultaneous increase of api gravity of heavy oils
US9637689B2 (en) 2011-07-29 2017-05-02 Saudi Arabian Oil Company Process for reducing the total acid number in refinery feedstocks
US20150210928A1 (en) * 2011-10-18 2015-07-30 Baker Hughes Incorporated Method for reducing hydrogen sulfide evolution from asphalt and heavy fuel oils
US9334448B2 (en) * 2011-10-18 2016-05-10 Baker Hughes Incorporated Method for reducing hydrogen sulfide evolution from asphalt and heavy fuel oils
US9238780B2 (en) 2012-02-17 2016-01-19 Reliance Industries Limited Solvent extraction process for removal of naphthenic acids and calcium from low asphaltic crude oil
EP2628780A1 (en) 2012-02-17 2013-08-21 Reliance Industries Limited A solvent extraction process for removal of naphthenic acids and calcium from low asphaltic crude oil
CN105220158A (en) * 2014-06-19 2016-01-06 中石化洛阳工程有限公司 Non-phosphor high-temperature inhibitor and preparation method thereof

Also Published As

Publication number Publication date Type
DE69312901D1 (en) 1997-09-11 grant
EP0607640A1 (en) 1994-07-27 application
EP0607640B1 (en) 1997-08-06 grant
JPH06240264A (en) 1994-08-30 application
JP2971691B2 (en) 1999-11-08 grant
ES2106959T3 (en) 1997-11-16 grant
DE69312901T2 (en) 1998-02-05 grant

Similar Documents

Publication Publication Date Title
US3915970A (en) Hexahydro-1,3,5-triazines
US5322640A (en) Water soluble corrosion inhibitors
US5744024A (en) Method of treating sour gas and liquid hydrocarbon
US5556451A (en) Oxygen induced corrosion inhibitor compositions
US3025313A (en) Amino-aldehyde condensation product
US4647589A (en) Inhibition of microbiological growth
WO1997045507A1 (en) Fuel additives
US4619756A (en) Method to inhibit deposit formation
US3364130A (en) Reducing fouling deposits in process equipment
US4842716A (en) Ethylene furnace antifoulants
US4024048A (en) Organophosphorous antifoulants in hydrodesulfurization
US3372009A (en) Liquid fuel compositions containing as anti-corrosion agent an alkyl monoalkanol amino compound
US4889614A (en) Methods for retarding coke formation during pyrolytic hydrocarbon processing
US4806229A (en) Volatile amines for treating refinery overhead systems
WO2004044266A1 (en) Metal corrosion inhibitor and hydrogen chloride formation inhibitor in a crude oil atmospheric distillation unit
US4024051A (en) Using an antifoulant in a crude oil heating process
US5468367A (en) Antifoulant for inorganic fouling
US5556575A (en) Corrosion inhibition in refineries using the reaction product of hydrocarbyl succinic anhydride and an amine
US4927519A (en) Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium using multifunctional antifoulant compositions
WO1995020637A2 (en) Hydrocarbon oil-aqueous fuel and additive compositions
US2944969A (en) Prevention of rust and corrosion
US5965785A (en) Amine blend neutralizers for refinery process corrosion
US5630964A (en) Use of sulfiding agents for enhancing the efficacy of phosphorus in controlling high temperature corrosion attack
US4313917A (en) Method of defoaming amine solutions
US5552085A (en) Phosphorus thioacid ester inhibitor for naphthenic acid corrosion

Legal Events

Date Code Title Description
AS Assignment

Owner name: EXXON CHEMICAL PATENTS, INC., NEW JERSEY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:PETERSEN, PHILIP R.;ROBBINS, FREDERICK R. III;WINSTON, WILLIAM G.;REEL/FRAME:006308/0942

Effective date: 19901219

AS Assignment

Owner name: WORCESTER COUNTY INSTITUTION FOR SAVINGS, MASSACHU

Free format text: SECURITY INTEREST;ASSIGNOR:MORGANA CONSTRUCTION COMPANY;REEL/FRAME:006406/0014

Effective date: 19920131

REMI Maintenance fee reminder mailed
SULP Surcharge for late payment
FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: NALCO/EXXON ENERGY CHEMICALS, LP, TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:EXXON CHEMICAL PATENTS, INC.;REEL/FRAME:008376/0134

Effective date: 19961024

FPAY Fee payment

Year of fee payment: 8

AS Assignment

Owner name: ONDEO NALCO ENERGY SERVICES, L.P., TEXAS

Free format text: CHANGE OF NAME;ASSIGNOR:NALCO/EXXON ENERGY CHEMICALS, L.P.;REEL/FRAME:012312/0854

Effective date: 20010614

AS Assignment

Owner name: CITICORP NORTH AMERICA, INC. AS ADMINISTRATIVE AGE

Free format text: GRANT OF SECURITY INTEREST;ASSIGNOR:ONDEO NALCO ENERGY SERVICES, L.P.;REEL/FRAME:014797/0293

Effective date: 20031104

FPAY Fee payment

Year of fee payment: 12

AS Assignment

Owner name: NALCO ENERGY SERVICES, L.P., TEXAS

Free format text: CHANGE OF NAME;ASSIGNOR:ONDEO NALCO ENERGY SERVICES, L.P.;REEL/FRAME:017045/0196

Effective date: 20031107

AS Assignment

Owner name: NALCO COMPANY, ILLINOIS

Free format text: MERGER;ASSIGNOR:NALCO ENERGY SERVICES, L.P.;REEL/FRAME:017303/0524

Effective date: 20060101

AS Assignment

Owner name: BANK OF AMERICA, N.A., AS COLLATERAL AGENT, NEW YO

Free format text: SECURITY AGREEMENT;ASSIGNORS:NALCO COMPANY;CALGON LLC;NALCO ONE SOURCE LLC;AND OTHERS;REEL/FRAME:022703/0001

Effective date: 20090513

Owner name: BANK OF AMERICA, N.A., AS COLLATERAL AGENT,NEW YOR

Free format text: SECURITY AGREEMENT;ASSIGNORS:NALCO COMPANY;CALGON LLC;NALCO ONE SOURCE LLC;AND OTHERS;REEL/FRAME:022703/0001

Effective date: 20090513

AS Assignment

Owner name: NALCO COMPANY, ILLINOIS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:BANK OF AMERICA, N.A.;REEL/FRAME:035976/0609

Effective date: 20111201

AS Assignment

Owner name: NALCO COMPANY, ILLINOIS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:BANK OF AMERICA, N.A.;REEL/FRAME:041808/0713

Effective date: 20111201

AS Assignment

Owner name: NALCO COMPANY LLC, DELAWARE

Free format text: CHANGE OF NAME;ASSIGNOR:NALCO COMPANY;REEL/FRAME:041835/0903

Effective date: 20151229

Owner name: NALCO COMPANY LLC, DELAWARE

Free format text: CHANGE OF NAME;ASSIGNOR:NALCO COMPANY;REEL/FRAME:041836/0364

Effective date: 20151231

Owner name: ECOLAB USA INC., MINNESOTA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NALCO COMPANY LLC;CALGON CORPORATION;CALGON LLC;AND OTHERS;REEL/FRAME:041836/0437

Effective date: 20170227

Owner name: NALCO COMPANY, ILLINOIS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITICORP NORTH AMERICA, INC.;REEL/FRAME:041837/0366

Effective date: 20170227

AS Assignment

Owner name: ECOLAB USA INC., MINNESOTA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NALCO COMPANY;REEL/FRAME:042147/0420

Effective date: 20170227